Antioxidative Composition For Feed Raw Material

ABSTRACT

The present invention is directed to a safe and inexpensive antioxidative composition being able to produce from relatively inexpensive raw material originated from natural resources, the antioxidative composition being excellent in effective antioxidation for a raw material for feed and food. This antioxidative composition comprises a distillate obtained from a production process of a vegetable oil, an oil-soluble-electron donor component and a viscosity reducing agent having a liquid oil derived form a plant.

BACKGROUND OF THE INVENTION

The present invention relates generally to a technique for prevention against oxidation of a raw material for feed and, more specifically, to an antioxidant composition to prevent oxidation of a raw material for feed, especially of fish meal (fish flour), effectively and safely.

Fish meal, like brown meals from colored fish as a raw material, such as sardines, anchovies, mackerels, bonitos, tunas and so on, or like white meals from white fish, such as flounders, cod fish and so on, is rich in amino acids and proteins such as lysine, methionine, myristic acid and so on, hence it is used widely and traditionally, as a raw material for feed, especially for livestock, poultry, farm fish or pet food.

Such fish meal as a raw material for feed contains about 8% of fish oil in fish meal and that is relatively easy to be oxidized, therefore, a specific antioxidative agent is generally added to it when it is distributed. Fish meal without an antioxidative agent of course causes deterioration during distribution or when it is stored and there is a risk of fire due to high temperature from oxidization reaction under a certain situation such as a circumstance when being transferred on a ship in the ocean or a circumstance like being stored under a relatively high temperature.

Conventionally, in order to prevent oxidation of such a raw material for feed, ethoxyquin (6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline) is used as an antioxidative agent. Ethoxyquin, being a synthesized antioxidative agent itself, is an excellent chemical as an antioxidative ability. In Japan, as an additive for a raw material for feed, it is approved to add it up to a fixed standard amount for additives (less than 150 ppm), however, it is not approved to add it as an additive to raw materials for food. Therefore, for safety issues for a raw material for pet food or for human bodies via meat from livestock or farm fish and so on, it is necessary to develop a safer antioxidative agent which can be substituted with ethoxyquin because conventional synthesized antioxidative agents are not necessarily good enough.

Conventionally, there are suggestions for various kinds of antioxidative agents stemming from natural resources. For example, it is known that there is an antioxidative agent of fish oil which is added with ethoxyquin, vitamin E and lecithin (Japanese Patent Laid-Open Publication No. 2001-323295), an antioxidative agent containing a lignane antioxidant (Japanese Patent Laid-Open Publication Nos. 2001-139579 and 2005-23125), an antioxidative agent using olive extract (Japanese Patent Laid-Open Publication No. 2001-181632), and a refining method for tocopherol having anti-oxidization action from soybean distillate (scum) and the like (Japanese Patent Laid-Open Publication No. 1985-149582).

Additionally, there are researches published about various kinds of ingredients for oxidization suppression from the point of view of using resources effectively which is bi-produced from a process of food manufacturing (Food and Development, Volume 28, No. 2, 1993; Extraction and Application of Novel Type of Antioxidants, in Particular, Isolated from Sesame Seed, Bio Ind., Vol. 10, No. 3, Page 141-148, 1993; Stereochemical structure of antioxidative bisepoxylignans, Sesaminol and its isomers, transformed from sesamolin, Agric Biol. Chem., Vol. 51, No. 5, Page 128501289, 1987; Lecture Summaries for the Conference of the Japanese Society of Fisheries Science, Vol. 1998, Page 117, 1998; Academic Report, Department of Agriculture, University of Mie, No. 72, Page 105-111, 1986; and Research Study about Materialization of Non-Used Resources Related to Food: Reviewing Effective Usage of Deodorization Distillate, Report from Fukuoka Prefecture).

However, antioxidative agents suggested in the past, have been found to not have long-term durability with an antioxidative effect for a raw material for feed; moreover, manufacturing cost is not satisfactory either. For example, tocopherol (Vitamin E) itself is known to have antioxidative ability and its refining method is also known (Japanese Patent Laid-Open Publication No. 1985-149582), however, refined tocopherol is expensive, thus it is not realistic to use it for a raw material for feed.

Moreover, antioxidative agents suggested in the past, because of their characteristics, it can be difficult to add them to a raw material for feed by spraying or sprinkling etc as they are, and it is a problem that it can't be applied easily in the usage procedure.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a safe and inexpensive antioxidative composition being able to produce from relatively inexpensive raw material originated from natural resources, the antioxidative composition being excellent in effective antioxidation for a raw material for feed and food.

The above object can be attained by an antioxidative composition for a raw material for food or feed, the antioxidative composition comprising a distillate obtained from a production process of a vegetable oil, an oil-soluble-electron donor component and a viscosity reducing agent comprising a liquid oil derived form a plant.

According to the preferable embodiment of the present invention, the distillate described above can be a deodorization distillate being by-produced from the production process of one of the vegetable oils at least one of the vegetable oils selected from the group consisting of soybean oil, rapeseed oil, rice oil, oba seed oil, shiso oil, sesame oil, coconut oil, cotton seed oil, sunflower oil, corn oil, safflower oil and palm oil; the oil-soluble-electron donor component comprises lecithin; and the liquid oil derived from a plant is selected from at least one of the group consisting of soy sauce oil, olive oil, soybean oil, rapeseed oil salad oil and medium chain triglycerides (MCT).

Further, in the preferable embodiment of the present invention, the composition can comprise 10 to 60 parts by weight of the distillate, 1 to 45 parts by weight of the oil-soluble-electron donor component, and 10 to 90 parts by weight of the liquid oil derived from a plant.

Furthermore, in the preferable embodiment of the present invention, the viscosity of the composition can be in the range between 0.1 dPa s and 1.0 dPa s.

The present invention includes a method for antioxidation of a raw material for food or feed, the method comprising spraying the antioxidative composition over the raw material for food or feed.

Further, the present invention includes a method for preparing a raw material for feed having a good antioxidative properties, the method comprising spraying the antioxidative composition over the raw material for food or feed, and includes the fish meal as a raw material for feed, the fish meal containing the antioxidative composition.

According to the present invention, it is extremely useful in the food industry because the antioxidative composition utilizes a distillate by-produced in the manufacturing process of vegetable oil for food, and combines the distillate with an oil-soluble-electron donor component and a liquid oil derived from a plant, whereby it is possible to provide an antioxidative composition for a raw material for feed and food inexpensively, that is excellent in durability with safe antioxidative properties, that can substitute the conventional synthesized ethoxyquin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 2 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 3 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 4 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 5 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 6 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 7 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 8 is a graph showing examples and comparative examples of the present invention based on experiments.

FIG. 9 is a graph showing examples and comparative examples of the present invention based on experiments.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

As is described above, the antioxidative composition according to the present invention is characterized in that the antioxidative composition comprises a distillate obtained from a production process of a vegetable oil, an oil-soluble-electron donor component and a viscosity reducing agent comprising a liquid oil derived form a plant. The components of the present invention will be explained as follows.

In the present invention, a distillate obtained from the manufacturing process of vegetable oil is used as an ingredient having an antioxidative ability. This type of distillate (extract residue or distillate) is a refined residual of a by-product from manufacturing process of vegetable oil. The distillate means a deodorization distillate by-produced from manufacturing vegetable oil such as soybean oil, rapeseed oil, rice oil, oba seed oil, shiso oil, sesame oil, coconut oil, cotton seed oil, sunflower oil, corn oil, safflower oil and palm oil.

For example, in the manufacturing process of soybean oil, usually, soybean crude oil is manufactured to be refined oil from the following procedures: process of excluding gum, process of drying, process of discoloring, process of excluding wax and process of deodorizing. Especially, a distillate (deodorization distillate) produced from a process of deodorizing can preferably be used as a distillate ingredient of the present invention. The deodorization distillate by-produced as such is consisted from sludge substance. In this distillate there is tocopherol of about 1 to 13 parts by weight, that has antioxidative ability. However, according to the present invention, deodorization distillate which is by-produced is used as a raw material, and it is convenient that it is unnecessary to separate tocopherol from distillate, and it is very advantageous in terms of manufacturing cost.

Soybean distillate conventionally is known to be highly safe and therefore it is used as a medicine for internal disorders or a supplement, which is mixed in feed as a form of fatty acid soap by adding a source of Ca.

In the present invention, the distillate describe above is combined with an oil-soluble-electron donor component and a liquid oil from a plant.

The oil-soluble-electron donor component according to the present invention can be a component to synergistically improve antioxidative action that tocopherol contained in the distillate originally has and the durability of its action by combining together with the distillate. Specifically, it is preferable to use lecithin, ascorbic acid, polyphenols, green tea extract, ascorbic acid fatty acid ester, cephaline, spermine or a combination appropriately chosen from them. In the present invention, among those described above, lecithin such as soybean lecithin, yolk lecithin and the like is especially preferable to be used. These components of oil-soluble-electron donor contribute to reduction reaction against a tocopherol ingredient that is radicalized by active oxygen, therefore it is assumed that antioxidative ability described above is improved and its durability is also improved.

Further, in the present invention, in addition to the ingredients described above, a liquid oil from a plant/vegetable is added as an essential component. The mixture of the distillate and the oil-soluble-electron donor component such as lecithin and the like has relatively high viscosity. Therefore, it is extremely difficult to spray it on the fish meal. Thus, in the present invention, a liquid oil from natural resources is added as a viscosity reducing agent.

As such a viscosity reducing agent, preferable one for the combination with two ingredients described above, can be at least one of the component selected from the group consisting of soy sauce oil, olive oil, soybean oil, rapeseed oil, oba seed oil, shiso oil and medium-chain triglyceride (MCT), and, especially, soy sauce oil is the most preferable to be used.

Soy sauce oil is a by-product produced from brewing process of soy sauce from whole soybeans primarily, as further details, it is a component of oil and fat, which is produced through a pressuring process in a procedure of manufacturing soy sauce by adding aspergillus oryzae with whole soybeans (soybeans which are not fat-free) and flour as ingredients. Soy sauce oil as a by-product from such soy sauce manufacturing process used to be disposed or burnt traditionally, however, in the present invention; it is very advantageous for an industry to use such a by-product effectively.

It is not necessarily clear that a reason for decreasing effectively with viscosity of combination of the deodorization distillate described above and the oil-soluble-electron donor component, in soy sauce oil, during its producing process, free fatty acids are included as main ingredients, which are produced from hydrolysis of soybean oil, and that is why it is considered that the viscosity is lower than regular vegetable oil.

Viscosity of an antioxidative composition for feed according to the present invention can be appropriately selected by a quality of the spraying device that is used for spraying. However, in general, it is preferable to be in the range of 0.1 dPa s to 1.0 dPa s, more preferably, it is in the range of 0.1 dPa s to 0.8 dPa s.

Further, in the present invention, from the point of creating antioxidative ability, improving durability and adjusting to a proper viscosity for spraying, the formulation ratio of the distillate, the oil-soluble-electron donor component and the liquid oil from a plant can preferably be in the range of: Distillate: 10 to 60 parts by weight, preferably 20 to 50 parts by weight; oil-soluble-electron donor component: 1 to 45 parts by weight, preferably 1 to 30 parts by weight; and a liquid oil from a plant: 10 to 90 parts by weight, preferably 20 to 60 parts by weight.

About 1 to 13 parts by weight of tocopherol is contained in a distillate. It is therefore preferable to add more than 130 ppm of tocopherol to the fish meal in order to suppress the oxidation of fish meal effectively. Thus, the amount of the distillate is greatly influenced by the amount of tocopherol contained therein. The distillate, however, contains ample amounts of unsaturated fatty acid, and it is not preferable to add more than 60 parts by weight of the distillate to the composition because it causes letting unsaturated fatty acid absorb many liquid layers, thereby decreasing the yield of manufacturing of antioxidative components and decreasing efficiency of handling.

It is preferable to add more oil-soluble-electron donor component in order to maintain antioxidative ability of the antioxidative composition, however, if it is added more than 45 parts by weight, it causes drastic increase of viscosity of the antioxidative composition. Thus, it is not preferable because it reduces the amount of the antioxidative composition sprayed or sprinkled.

Furthermore, when less than 10 parts by weight of the liquid oil from a plant is added, it makes difficult to disperse other components uniformly in the composition. On the other hand, it is not preferable to add more than 90 parts by weight of the liquid oil because it is difficult to obtain enough amount of the distillate.

In the present invention, one of the most preferable embodiments is: soybean distillate: lecithin: soy sauce oil=2:1:1 as a formulation ratio, and supernatant fluids of this mixture can be used as a spraying antioxidative composition.

The present invention includes a method for antioxidation of a raw material for food or feed, the method comprising spraying the antioxidative composition over the raw material for food or feed.

Further, the present invention includes a method for preparing a raw material for feed having a good antioxidative properties, the method comprising spraying the antioxidative composition over the raw material for food or feed, and includes the fish meal as a raw material for feed, the fish meal containing the antioxidative composition.

As for a raw material for feed applied with the antioxidative composition according to the present invention, it is not especially limited; however, any materials that generally need to be antioxidated can be used as a raw material for feed. Typically, it can preferably be used for a fish meal for a raw material for feed. Thus, the present invention includes a fish meal as a raw material for feed, the fish meal containing the antioxidative composition according to the present described above.

EXAMPLES

Examples and comparative examples of the present invention are now further described in detail based on the experimental examples as follows.

Experiment 1

Inside of an autoclave with an inner volume of 130 ml, a beaker is set with 40 g of fish meal (produced from bonito), which is combined equally with various materials shown in Table 1. After it is tightly closed, it is connected with an oxygen tank to make inner pressure of 345 kPa by adding oxygen. This autoclave is left for 72 hours in a machine with a fixed temperature of 60° C., and after 72 hours, the pressure is read, and the difference from the initial value corresponds to the amount of oxygen absorbed by the 40 g of fish meal. Results are shown in FIG. 1.

TABLE 1 Component Weight ratio 1 Control (nothing added) — 2 Soy sauce oil  500 ppm 3 Soybean lecithin ^(#)  500 ppm 4 Soybean distillate 1,000 ppm 5 Soy sauce oil + lecithin (combining ratio: 1:1) 1,000 ppm 6 Soy sauce oil + lecithin + soybean distillate 2,000 ppm (Combining ratio: 1:1:2) ^(#) hereinafter it is called “lecithin”.

As a result, it is found that a strong antioxidative ability of fish meal appeared by combining three ingredients, which are soy sauce oil, lecithin, soybean distillate (tocopherol amount contained (w/w): 12.23%).

Experiment 2

Combine uniformly with fluid layers of an antioxidative agent manufactured from various ingredients shown in Chart 2 (amount to be added is 1,000 ppm to 6,000 ppm) and 40 g of fish meal (produced from bonito), and put them in a beaker. This beaker is set in an autoclave with an inner volume of 130 ml. After the autoclave is closed tightly, it is connected with an oxygen tank to make the inner pressure at 345 kPa by adding oxygen. This autoclave is left for 36 hours in a machine with a fixed temperature of 98° C. After 36 hours the pressure is read, and the difference from the initial value corresponds to the amount of oxygen absorbed by the 40 g of fish meal. Results are shown in FIG. 2.

TABLE 2 Name of ingredients Weight ratio 1 Soy sauce oil 25 2 Lecithin 25 3 Soybean distillate (amount of tocopherol contained 50 (w/w): 12.23%)

As a result, by adding 2,000 ppm of an antioxidative agent shown in Table 2 (the amount of tocopherol added is 260 ppm), it is found that it is possible to obtain the same antioxidative ability as ethoxyquin with the fish meal.

Experiment 3

Inside an autoclave with an inner volume of 130 ml, a beaker is set with 40 g of fish meal (produced from bonito), which is sprinkled with fluid layers of various materials shown in Table 3. After it is tightly closed, it is connected with an oxygen tank to make the inner pressure at 345 kPa by adding oxygen. This autoclave is left for 72 hours in a machine with a fixed temperature of 60° C. After 72 hours the pressure is read, and the difference from the initial value corresponds to the amount of the oxygen absorbed by the 40 g of fish meal. Results are shown in FIG. 3.

TABLE 3 Amount added Name to fish meal 1 Control (nothing added) — 2 Soy sauce oil + lecithin + soybean distillate ¹⁾  2,000 ppm (Mixture ratio: 1:1:2) 3 Soy sauce oil + lecithin + rape seed oil & soybean  4,000 ppm distillate ²⁾ (Mixture ratio: 1:1:2) 4 Soy sauce oil + lecithin + rice distillate ³⁾ 10,000 ppm (Mixture ratio: 1:1:2) ¹⁾ Amount of tocopherol contained (w/w): 12.23%, ²⁾ amount of tocopherol contained (w/w): 7.65%, ³⁾ amount of tocopherol contained (w/w): 2.30% (Measurements of tocopherol contained were implemented with experimental methods of standard oil fat analysis by Japan Oil Chemists' Society “2.4.10-1996 Tocopherol”.)

It is found that there is a strong antioxidative ability even when any type of distillate is added to the fish meal.

Experiment 4

Antioxidant-produced agents (with fluid layers of soy sauce oil+lecithin+soybean distillate (combination ratio is 1:1:2) is added to fish meal for 2,000 ppm, 4,000 ppm, 6,000 ppm, 8,000 ppm, 10,000 ppm or ethoxyquin 150 ppm is added to fish meal respectively. This fish meal is stored in a machine with a fixed temperature of 60° C. for five weeks. During these five weeks, sampling is implemented at week 2, week 3, week 4 and week 5. Fish oil is extracted from the fish meal, sampled with the Bligh & Dyer method, peroxide value (POV) (FIG. 4) of this fish oil and the residual amount of tocopherol (FIG. 5) are measured. These measurements are based on the experimental methods for standard oil fat analysis provided by Japan Oil Chemists' Society.

As a result, all the fish meal is suppressed to be oxidized. There was tocopherol remaining that was added to the fish meal, even after five weeks of storage. Therefore, it is found that it is possible to suppress the antioxidation of fish meal effectively with a developed agent during transportation of actual fish meal. (It takes about one month for fish meal to be transported from South America to the Northern Hemisphere. 60° C. is the highest temperature in a container when a ship is crossing the equator.)

Experiment 5

As composition A, soy sauce oil: lecithin: =1:1 mixture (combined with weight ratio), as composition B, generic salad oil: lecithin=1:1 mixture (combined with weight ratio) are prepared, these are mixed with the combination ratio shown in FIG. 4. After being mixed, viscosities of various mixtures are measured by a B type spinning viscosity scale. Continuously, put these mixtures into a spray gun with suction. The amount sprayed is measured when mixtures are sprayed with air pressure of 0.4 MPas for 30 seconds. Results are shown in Table 4. The relations of viscosity and the amount sprayed are shown in FIG. 6 as well.

As a result, it is found that the amount sprayed goes down as the viscosity increases.

TABLE 4 A:B (Weight ratio) Type of value A only 1:5 2:4 3:3 4:2 5:1 B only Viscosity 0.75 0.75 0.8 0.98 1.45 1.8 2.4 (dPa · s) Amount sprayed 23.2 23.5 17.2 19.6 15.1 11 6.8 (g/30 s) A: soy sauce oil:lecithin = 1:1 mixture (Weight ratio) B: generic salad oil:lecithin = 1:1 mixture (Weight ratio)

Experiment 6

The changes of viscosity when lecithin is added to generic salad oil, soy sauce oil and medium-chain triglyceride (MCT) are measured by a B type spinning viscosity scale (FIG. 7).

As a result, it is found that there is a drastic increase of viscosity with soy sauce oil and MCT when the ratio of the amount of lecithin goes over 45%, and it is found that viscosity increase is suppressed when lecithin is added to soy sauce oil and MCT, in comparison to the case of adding it to salad oil.

Experiment 7

By using a production line of fish meal, three kinds of fish meal were prepared: (1) fish meal which was sprayed with 3,000 ppm (195 ppm as for the spray amount of tocopherol) of developing antioxidant formulation (soy sauce oil+lecithin+soybean distillate (mixing ratio: 1:1:2), (2) fish meal sprayed with 150 ppm of ethoxyquin, (3) fish meal which was nothing added (a control). Each prepared fish meal was stored in 500 kg of a jute bag for fish meal transportation; those bags were stored in a storage place for two weeks. The average temperature when stored was 31° C. 50 g of fish meal stored in a jute bag (a 500 kg jute bag) was sampled from three different locations. Then, a lipid was extracted from sampled fish meal, and peroxide value (meq/kg) of each extracted lipid was measured. Additionally, a data logger was added to a jute bag to measure changes of temperature of the fish meal immediately after it was produced and those of the 2-week-old fish meal.

FIG. 8 shows the changes of oxidizing rate (average values and standard deviation of each three values) of three different kinds of fish meal and FIG. 9 shows temperature changes of fish meal as a control when it was stored. From FIG. 9, temperature of fish meal was reached at 55° C. immediately after it was produced, and temperature went down around to the room temperature 1 to 2 week after the fish meal was produced. Form storage test results (FIG. 8), it was found that fish meal without antioxidant in one week after it was produced was strongly oxidized ((3) fish meal as a control). As opposed to it, (1) Fish meal containing developing antioxidant formulation, and (2) fish meal containing ethoxyquin suppressed early oxidization and we have found that both of them are effective antioxidants against oxidization of fish meal. 

1. An antioxidative composition for a raw material for food or feed, the antioxidative composition comprising a distillate obtained from a production process of a vegetable oil, an oil-soluble-electron donor component and a viscosity reducing agent comprising a liquid oil derived form a plant, provided that the oil-soluble-electron donor component excludes an ascorbic acid and ascorbyl palmitate.
 2. The antioxidative composition for a raw material for food or feed according to claim 1, wherein the distillate comprises a deodorization distillate being a by-product from a production process of at least one of the vegetable oils selected from the group consisting of soybean oil, rapeseed oil, rice oil, oba seed oil, shiso oil, sesame oil, coconut oil, cotton seed oil, sunflower oil, corn oil, safflower oil and palm oil.
 3. The antioxidative composition for a raw material for food or feed according to claim 1, wherein the oil-soluble-electron donor component comprises lecithin.
 4. The antioxidative composition for a raw material for food or feed according to claim 1, wherein the liquid oil derived from a plant is selected from at least one of the group consisting of soy sauce oil, olive oil, soybean oil, rapeseed oil salad oil and medium chain triglycerides (MCT).
 5. The antioxidative composition for a raw material for food or feed according to any one of claims 1-4, wherein the composition comprises 10 to 60 parts by weight of the distillate, to 45 parts by weight of the oil-soluble-electron donor component, and 10 to 90 parts by weight of the liquid oil derived from a plant.
 6. The antioxidative composition for a raw material for food or feed according to any one of claims 1-5, wherein the viscosity of the composition is in the range between 0.1 dPa s and 1.0 dPa s.
 7. The antioxidative composition for a raw material for food or feed according to any one of claims 1-6, wherein the composition consisting essentially of liquid parts excluding solid materials.
 8. A method for antioxidation of a raw material for food or feed, the method comprising spraying the antioxidative composition according to any one of claims 1-7 over the raw material for food or feed.
 9. A method for preparing a raw material for food or feed having a good antioxidative properties, the method comprising spraying the antioxidative composition according to any one of claims 1-7 over the raw material for food or feed.
 10. The method according to claim 8 or 9, wherein the raw material comprises a fish meal.
 11. A fish meal as a raw material for feed, the fish meal containing the antioxidative composition according to any one of claims 1 to
 7. 